JP5097928B2 - Method for producing tetraazaporphyrin compound - Google Patents
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- -1 tetraazaporphyrin compound Chemical class 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 39
- 150000001264 acyl cyanides Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003480 eluent Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NPBLQPWAISGYEU-UHFFFAOYSA-N 2,2-dimethylpropanoyl cyanide Chemical compound CC(C)(C)C(=O)C#N NPBLQPWAISGYEU-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- DAVJMKMVLKOQQC-UHFFFAOYSA-N 2-(2-fluorophenyl)acetonitrile Chemical compound FC1=CC=CC=C1CC#N DAVJMKMVLKOQQC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 150000001793 charged compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- YKENVNAJIQUGKU-UHFFFAOYSA-N tetraazaporphin Chemical class C=1C(C=N2)=NC2=NC(NN2)=NC2=CC(C=C2)=NC2=CC2=NC=1C=C2 YKENVNAJIQUGKU-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MRDUURPIPLIGQX-UHFFFAOYSA-N 2-(2-chlorophenyl)acetonitrile Chemical compound ClC1=CC=CC=C1CC#N MRDUURPIPLIGQX-UHFFFAOYSA-N 0.000 description 1
- OQRMWUNUKVUHQO-UHFFFAOYSA-N 2-naphthalen-1-ylacetonitrile Chemical compound C1=CC=C2C(CC#N)=CC=CC2=C1 OQRMWUNUKVUHQO-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WGGXUXVKEPYLHS-MSUUIHNZSA-N CC(C)(C)/C(/C#N)=C(\c1cccc2ccccc12)/C#N Chemical compound CC(C)(C)/C(/C#N)=C(\c1cccc2ccccc12)/C#N WGGXUXVKEPYLHS-MSUUIHNZSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
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- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、光記録用色素、光学フィルター用色素などとして有用なテトラアザポルフィリン化合物の製造法に関するものである。 The present invention relates to a method for producing a tetraazaporphyrin compound useful as a dye for optical recording, a dye for optical filters, and the like.
光記録用色素、光学フィルター用色素などとして有用なテトラアザポルフィリン化合物化合物は、下記の文献に開示されている。
本発明は、１，２−ジシアノエチレン化合物の２つの異性体のうちシス体の生成比率の高い製法を探求し、ひいてはテトラアザポルフィリン化合物の収率よい製法を提供せんとするものである。 The present invention seeks a process for producing a high cis isomer among the two isomers of 1,2-dicyanoethylene compound, and therefore provides a process for producing a tetraazaporphyrin compound with high yield.
即ち本発明は、一般式（１）で示されるアシルシアニドと一般式（２）で示される１置換アセトニトリル誘導体とを、酸性触媒及び塩基性触媒の存在下に脱水反応させることにより一般式（３）で示される１，２−ジシアノエチレン化合物のシス体を製造し、次いでこの１，２−ジシアノエチレン化合物のシス体を環化してテトラアザポルフィリン化合物を製造する方法において、酸性触媒として前記したアシルシアニドの１．５〜２倍当量に相当する四塩化チタンを用いると共に、塩基性触媒として前記したアシルシアニドの２．８〜４倍当量に相当するＮ−メチルモルホリンを使用することを特徴とするテトラアザポルフィリン化合物の製造法に係るものである。
以下の構造式において、Ｒはオルト位にハロゲンが置換したフェニル基又は無置換のナフチル基を意味する。
That is, in the present invention, the acyl cyanide represented by the general formula (1) and the 1-substituted acetonitrile derivative represented by the general formula (2) are subjected to a dehydration reaction in the presence of an acidic catalyst and a basic catalyst, whereby the general formula (3) In the method of producing a tetraazaporphyrin compound by cyclization of the cis isomer of 1,2-dicyanoethylene compound represented by the following formula, and then cyclizing the cis isomer of 1,2-dicyanoethylene compound, Tetraazaporphyrin characterized by using titanium tetrachloride corresponding to 1.5 to 2 equivalents and using N-methylmorpholine corresponding to 2.8 to 4 equivalents of acyl cyanide as a basic catalyst. This relates to a method for producing a compound.
In the following structural formulas, R means a phenyl group substituted with a halogen at the ortho position or an unsubstituted naphthyl group.
一般式（３）で示される１，２−ジシアノエチレン化合物のシス体は、塩化亜鉛、塩化アルミニウムなどでは得られない。シス体を収率よく得るために、本発明では、酸性触媒として四塩化チタンを用い、塩基性触媒としてＮ−メチルモルホリンを用いる。
A cis isomer of the 1,2-dicyanoethylene compound represented by the general formula (3) cannot be obtained with zinc chloride, aluminum chloride or the like. In order to obtain a cis isomer with good yield, in the present invention, titanium tetrachloride is used as an acidic catalyst and N-methylmorpholine is used as a basic catalyst.
「特許文献２」の実施例では、いずれの場合もアシルシアニドの３倍当量に相当する酸性触媒と、６倍当量に相当する塩基性触媒を使用している。
一般式（３）で示される１，２−ジシアノエチレン化合物のシス体の生成比率を高めるために、本発明ではアシルシアニドの１．５〜２倍当量に相当する量の四塩化チタンを使用し、アシルシアニドの２．８〜４倍当量に相当する量のＮ−メチルモルホリンを使用する。
因みに、アシルシアニド誘導体とモノハロゲノアセトニトリルとの脱水縮合反応により下記の様な１，２−ジシアノエチレン化合物のシス体を得ようとする場合には、四塩化チタンやＮ−メチルモルホリンの使用量を変えてもシス体、トランス体の生成比率は殆ど変わらず、テトラアザポルフィリン化合物の製造に有効なシス体の生成比率は極めて低い。
In each example of “Patent Document 2”, an acidic catalyst corresponding to 3 times equivalent of acyl cyanide and a basic catalyst corresponding to 6 times equivalent of acyl cyanide are used.
In order to increase the production ratio of the cis isomer of the 1,2-dicyanoethylene compound represented by the general formula (3), the present invention uses an amount of titanium tetrachloride corresponding to 1.5 to 2 equivalents of acyl cyanide, An amount of N-methylmorpholine corresponding to 2.8 to 4 equivalents of acyl cyanide is used.
By the way, when trying to obtain a cis isomer of 1,2-dicyanoethylene compound as shown below by dehydration condensation reaction of acyl cyanide derivative and monohalogenoacetonitrile, the amount of titanium tetrachloride or N-methylmorpholine used is changed. However, the production ratio of the cis isomer and the trans isomer is hardly changed, and the production ratio of the cis isomer effective for the production of the tetraazaporphyrin compound is extremely low.
目的とするテトラアザポルフィリン化合物は、前記シス体、又はシス体／トランス体混合物と金属又は金属誘導体とをアルコール系溶媒中で有機塩基共存下で加熱反応することにより得ることが出来る。
上記の反応により得られるテトラアザポルフイリン化合物には、理論的に次の（４−１）〜（４−４）式で示される４種の異性体が存在する。
The target tetraazaporphyrin compound can be obtained by subjecting the cis isomer or cis isomer / trans isomer mixture and a metal or metal derivative to a heat reaction in the presence of an organic base in an alcohol solvent.
In the tetraazaporphyrin compound obtained by the above reaction, there are theoretically four kinds of isomers represented by the following formulas (4-1) to (4-4).
本発明によれば、１，２−ジシアノエチレン化合物に占めるシス体の比率を格段に大きくすることができ、ひいては最終目的物であるテトラアザポルフィリン化合物を収率よく得ることができる。 According to the present invention, the ratio of the cis isomer to the 1,2-dicyanoethylene compound can be remarkably increased, and as a result, the tetraazaporphyrin compound, which is the final target product, can be obtained with high yield.
１，２−ジシアノエチレン化合物に占めるシス体の比率は、前記したアシルシアニドに対する四塩化チタンの使用量とＮ−メチルモルホリンの使用量が少なければ少ないほど大きくなる傾向にある。しかしながら、これらの使用量が少なくなると反応が進まず、未反応物が増加してくるため、ひいては最終目的物の収率が悪くなる。
四塩化チタンの望ましい使用量は、前記したアシルシアニドの１．５〜２倍当量に相当する量であり、Ｎ−メチルモルホリンの望ましい使用量は、前記したアシルシアニドの２．８〜４倍当量に相当する量である。
The ratio of the cis form in the 1,2-dicyanoethylene compound tends to increase as the amount of titanium tetrachloride and the amount of N-methylmorpholine used relative to the acyl cyanide decreases. However, when the amount of these used decreases, the reaction does not proceed and unreacted substances increase, resulting in a poor yield of the final target product.
Four desirable amount of titanium tetrachloride is an amount equivalent to 1.5 to 2 times equivalent amount of acyl cyanide mentioned above, desirable amount of N- methyl morpholine, of acyl cyanides mentioned above 2.8 to 4 An amount corresponding to a double equivalent.
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン２８．４ｇ（０．１５０ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−フルオロベンジルシアニド１３．５ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン３０．３ｇ（０．３００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１５時間撹拌した。反応混合物を氷水３５０ｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、ヘキサン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して粗製の化合物（ａ）をそのトランス体との混合物として２１．７ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 28.4 g (0.150 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 13.5 g (0.100 mol) of 2-fluorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 30.3 g (0.300 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, the temperature of the mixture was returned to room temperature, and the mixture was stirred for 15 hours. The reaction mixture was diluted with 350 ml of ice water and the diluted solution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of hexane and 45 g of activated clay were added, and the mixture was stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 21.7 g of crude compound (a) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７３．８％、トランス体１５．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を１６．０ｇ（収率７０．２％）得た。ｍｐ：１０１〜１０２℃。ＭＳ：Ｍ＋＝２２８（分子イオン）。１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）：δ１．１５ｐｐｍ（ｓ，９Ｈ），δ７．１４〜７．２９（ｍ，３Ｈ），δ７．４４〜７．５３（ｍ，１Ｈ）。As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 73.8% cis isomer and 15.3% trans isomer. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 16.0 g of compound (a) (yield: 70.2%). mp: 101-102 ° C. MS: M <+> = 228 (molecular ion). 1 H-NMR (300 MHz, CDCl 3 ): δ 1.15 ppm (s, 9H), δ 7.14-7.29 (m, 3H), δ 7.44-7.53 (m, 1H).
反応条件、及び後処理条件を全て実施例１と同様に行い、粗製の化合物（ａ）をそのトランス体との混合物として２１．８ｇ得た。得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７３．５％、トランス体１５．５％であった。これをエタノール２７ｍｌに加熱溶解し、この溶液を徐々に０℃まで冷却して、この温度で３０分撹拌した。晶析物をろ集し、冷エタノールで洗浄、５０℃で乾燥して化合物（ａ）を１２．５ｇ（収率５５．０％）得た。ＧＣ測定の結果、クロマトグラフ上で占める面積比は９８％であった。 Reaction conditions and post-treatment conditions were all carried out in the same manner as in Example 1 to obtain 21.8 g of the crude compound (a) as a mixture with its trans isomer. As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 73.5% cis isomer and 15.5% trans isomer. This was dissolved by heating in 27 ml of ethanol, and the solution was gradually cooled to 0 ° C. and stirred at this temperature for 30 minutes. The crystallized product was collected by filtration, washed with cold ethanol, and dried at 50 ° C. to obtain 12.5 g (yield 55.0%) of compound (a). As a result of GC measurement, the area ratio occupied on the chromatograph was 98%.
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン３７．９ｇ（０．２００ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−フルオロベンジルシアニド１３．５ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン４０．４ｇ（０．４００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、実施例１と同様の操作を施して粗製の化合物（ａ）をそのトランス体との混合物として２１．８ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 37.9 g (0.200 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 13.5 g (0.100 mol) of 2-fluorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 40.4 g (0.400 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the same operation as in Example 1 was performed to obtain 21.8 g of a crude compound (a) as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７２．５％、トランス体１７．６％であった。トルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を１４．９ｇ（収率６５．３％）得た。 As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was cis isomer 72.5% and trans isomer 17.6%. Purification was performed by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 14.9 g (yield: 65.3%) of compound (a).
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン２８．４ｇ（０．１５０ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−クロロベンジルシアニド１５．２ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン３０．３ｇ（０．３００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１２時間撹拌した。反応混合物を氷水３５ｏｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、ヘキサン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して化合物（ｂ）をそのトランス体との混合物として２２．０ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 28.4 g (0.150 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 15.2 g (0.100 mol) of 2-chlorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 30.3 g (0.300 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 12 hours. The reaction mixture was diluted with 35 ml of ice water and the dilution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of hexane and 45 g of activated clay were added, and the mixture was stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 22.0 g of compound (b) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７７．２％、トランス体１８．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を１７．６ｇ（収率７２．０％）得た。ＭＳ：Ｍ＋＝２４４（分子イオン）。As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 77.2% cis isomer and 18.3% trans isomer. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 17.6 g of compound (a) (yield 72.0%). MS: M + = 244 (molecular ion).
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン２８．４ｇ（０．１５０ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて１−ナフチルアセトニトリル１６．７ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン３０．３ｇ（０．３００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１４時間撹拌した。反応混合物を氷水３５０ｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、トルエン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して粗製の化合物（ｃ）をそのトランス体との混合物として２４．７ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 28.4 g (0.150 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or lower, and then 16.7 g (0.100 mol) of 1-naphthylacetonitrile was added dropwise at 0 ° C. or lower. Next, 30.3 g (0.300 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 14 hours. The reaction mixture was diluted with 350 ml of ice water and the diluted solution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of toluene and 45 g of activated clay were added, stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 24.7 g of crude compound (c) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７０．０％、トランス体１３．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ｃ）を１８．７ｇ（収率７２．０％）得た。ＭＳ：Ｍ＋＝２６０（分子イオン）。As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 70.0% cis isomer and 13.3% trans isomer. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 18.7 g (yield 72.0%) of compound (c). MS: M + = 260 (molecular ion).
撹拌機、冷却管、温度計を取り付けた四ツ口反応フラスコに化合物（ａ）２．２８ｇ（０．０１００ｍｏｌ）、塩化銅（Ｉ）０．３３ｇ（０．００３３ｍｏｌ）、及び１−ペンタノール３０ｍｌを仕込み、この混合物を窒素気流下で１００℃に昇温し、この温度でＤＢＵ１．５２ｇ（０．０１００ｍｏｌ）を３０分かけて滴下した。滴下終了後、この混合物を１２５℃に昇温して、この温度で窒素気流下８時間撹拌した。放冷後、反応混合物をメタノール１００ｍｌで希釈して、この希釈液に撹拌下で水５０ｍｌを滴下して色素を晶析させた。これをろ集、メタノール／水＝２／１で洗浄後、１００℃で乾燥して２．０１ｇの青紫色結晶を得た。これをヘキサン／トルエン＝１０／１〜１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製して色素（ａ）−１〜（ａ）−４の混合物を１．４６ｇ（収率６０．０％）得た。この４種の異性体混合物のクロロホルム中でのλｍａｘは５９３．５ｎｍ、モル吸光係数εは１３５０００であった。 In a four-necked reaction flask equipped with a stirrer, a condenser, and a thermometer, compound (a) 2.28 g (0.0100 mol), copper (I) chloride 0.33 g (0.0033 mol), and 1-pentanol 30 ml The mixture was heated to 100 ° C. under a nitrogen stream, and 1.52 g (0.0100 mol) of DBU was added dropwise at this temperature over 30 minutes. After completion of dropping, the mixture was heated to 125 ° C. and stirred at this temperature for 8 hours under a nitrogen stream. After allowing to cool, the reaction mixture was diluted with 100 ml of methanol, and 50 ml of water was added dropwise to the diluted solution with stirring to crystallize the dye. This was collected by filtration, washed with methanol / water = 2/1, and dried at 100 ° C. to obtain 2.01 g of blue-violet crystals. This was purified by silica gel column chromatography using hexane / toluene = 10/1 to 1/1 as an eluent to obtain 1.46 g (yield 60.0) of a mixture of dyes (a) -1 to (a) -4. %)Obtained. Λmax of these four isomer mixtures in chloroform was 593.5 nm and molar extinction coefficient ε was 135,000.
撹拌機、冷却管、温度計を取り付けた四ツ口反応フラスコに化合物（ｂ）２．４４ｇ（０．０１００ｍｏｌ）、塩化銅（Ｉ）０．３３ｇ（０．００３３ｍｏｌ）、及び１−ペンタノール３０ｍｌを仕込み、この混合物を窒素気流下で１００℃に昇温し、この温度でＤＢＵ１．５２ｇ（０．０１００ｍｏｌ）を３０分かけて滴下した。滴下終了後、この混合物を１２５℃に昇温して、この温度で窒素気流下７時間撹拌した。放冷後、反応混合物をメタノール１００ｍｌで希釈して、この希釈液に撹拌下で水３０ｍｌを滴下して色素を晶析させた。これをろ集、メタノール／水＝３／１で洗浄後、１００℃で乾燥して２．０３ｇの青紫色結晶を得た。これをヘキサン／トルエン＝１０／１〜１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製して色素（ｂ）−１〜（ｂ）−４の混合物を１．５１ｇ（収率５８．０％）得た。この４種の異性体混合物のクロロホルム中でのλｍａｘは５９３．５ｎｍ、モル吸光係数εは１２４０００であった。 In a four-necked reaction flask equipped with a stirrer, a condenser, and a thermometer, 2.44 g (0.0100 mol) of compound (b), 0.33 g (0.0033 mol) of copper (I) chloride, and 30 ml of 1-pentanol. The mixture was heated to 100 ° C. under a nitrogen stream, and 1.52 g (0.0100 mol) of DBU was added dropwise at this temperature over 30 minutes. After completion of the dropwise addition, the mixture was heated to 125 ° C. and stirred at this temperature for 7 hours under a nitrogen stream. After allowing to cool, the reaction mixture was diluted with 100 ml of methanol, and 30 ml of water was added dropwise to the diluted solution with stirring to crystallize the dye. This was collected by filtration, washed with methanol / water = 3/1, and dried at 100 ° C. to obtain 2.03 g of blue-violet crystals. This was purified by silica gel column chromatography using hexane / toluene = 10/1 to 1/1 as an eluent to obtain 1.51 g of a mixture of dyes (b) -1 to (b) -4 (yield 58.0). %)Obtained. Λmax in chloroform of this mixture of four isomers was 593.5 nm, and the molar extinction coefficient ε was 124000.
撹拌機、冷却管、温度計を取り付けた四ツ口反応フラスコに化合物（ｃ）３．００ｇ（０．０１１５ｍｏｌ）、ホルムアミド１．０４ｇ（０．０２３０ｍｏｌ）、三塩化バナジウム０．７２ｇ（０．００４６ｍｏｌ）、及び１−ペンタノール２５ｍｌを仕込み、この混合物を窒素気流下で７５℃に昇温し、この温度でＤＢＵ１．４０ｇ（０．００９２０ｍｏｌ）を４５分かけて滴下した。滴下終了後、この混合物を１２０℃に昇温して、この温度で窒素気流下１８時間撹拌した。放冷後、反応混合物をメタノール１００ｍｌで希釈して、この希釈液に撹拌下で水１５ｍｌを滴下して色素を晶析させた。これをろ集、メタノール／水＝３／１で洗浄後、１００℃で乾燥して２．４０ｇの青色結晶を得た。これをヘキサン／トルエン＝５／１〜１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製して色素（ｃ）−１〜（ｃ）−４の混合物を１．９３ｇ（収率６０．６％）得た。この４種の異性体混合物のクロロホルム中でのλｍａｘは６０９．０ｎｍ、モル吸光係数εは１３１０００であった。 Compound (c) 3.00 g (0.0115 mol), formamide 1.04 g (0.0230 mol), vanadium trichloride 0.72 g (0.0046 mol) in a four-necked reaction flask equipped with a stirrer, condenser, and thermometer ) And 25 ml of 1-pentanol, the mixture was heated to 75 ° C. under a nitrogen stream, and 1.40 g (0.00920 mol) of DBU was added dropwise at this temperature over 45 minutes. After completion of the dropwise addition, the mixture was heated to 120 ° C. and stirred at this temperature for 18 hours under a nitrogen stream. After allowing to cool, the reaction mixture was diluted with 100 ml of methanol, and 15 ml of water was added dropwise to the diluted solution with stirring to crystallize the dye. This was collected by filtration, washed with methanol / water = 3/1, and then dried at 100 ° C. to obtain 2.40 g of blue crystals. This was purified by silica gel column chromatography using hexane / toluene = 5/1 to 1/1 as an eluent to obtain 1.93 g of a mixture of dyes (c) -1 to (c) -4 (yield 60.6). %)Obtained. Λmax of this four isomer mixture in chloroform was 609.0 nm, and the molar extinction coefficient ε was 131000.
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン５６．９ｇ（０．３００ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−フルオロベンジルシアニド１３．５ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン６０．７ｇ（０．６００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１６時間撹拌した。反応混合物を氷水３５０ｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、ヘキサン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して粗製の化合物（ａ）をそのトランス体との混合物として２１．１ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 56.9 g (0.300 mol) of titanium tetrachloride, and this mixture was charged in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 13.5 g (0.100 mol) of 2-fluorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 60.7 g (0.600 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 16 hours. The reaction mixture was diluted with 350 ml of ice water and the diluted solution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of hexane and 45 g of activated clay were added, and the mixture was stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 21.1 g of crude compound (a) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体４５．０％、トランス体３５．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を９．７１ｇ（収率４２．６％）得た。 As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was cis isomer 45.0% and trans isomer 35.3%. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 9.71 g (yield 42.6%) of compound (a).
Claims (1)
以下の構造式において、Ｒはオルト位にハロゲンが置換したフェニル基又は無置換のナフチル基を意味する。
In the following structural formulas, R means a phenyl group substituted with a halogen at the ortho position or an unsubstituted naphthyl group.
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